WO2019230842A1 - Procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène - Google Patents

Procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène Download PDF

Info

Publication number
WO2019230842A1
WO2019230842A1 PCT/JP2019/021400 JP2019021400W WO2019230842A1 WO 2019230842 A1 WO2019230842 A1 WO 2019230842A1 JP 2019021400 W JP2019021400 W JP 2019021400W WO 2019230842 A1 WO2019230842 A1 WO 2019230842A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
chloro
distillation
hexafluoro
dycc
Prior art date
Application number
PCT/JP2019/021400
Other languages
English (en)
Japanese (ja)
Inventor
卓也 岩瀬
聡史 河口
高木　洋一
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2020522270A priority Critical patent/JP7314934B2/ja
Priority to CN201980035670.8A priority patent/CN112204003B/zh
Publication of WO2019230842A1 publication Critical patent/WO2019230842A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

  • the present invention relates to a method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene.
  • Hydrochlorofluorocarbons have a negative impact on the ozone layer and are therefore expected to be regulated.
  • HCFC 3,3-dichloro-1,1,1,2,2-pentafluoropropane (CF 3 -CF 2 -CHCl 2 , HCFC-225ca), 1,3-dichloro-1,1,2, 2,3-pentafluoropropane (CClF 2 —CF 2 —CHFCl, HCFC-225cb) and the like can be given.
  • HCFC regulations development of alternative compounds is desired.
  • HCFC 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene
  • CHCl CF—CF 2 —CF 2 —CF 2 H, HCFO-1437 dycc
  • 1437 dycc has a low global warming potential (GWP), and is expected as a compound suitable for applications such as cleaning agents, solvents, refrigerants, foaming agents, and aerosols.
  • GWP global warming potential
  • Non-Patent Document 1 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (hereinafter referred to as “OFPO”) is reacted with dichlorotriphenylphosphorane.
  • -Chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448 occc; hereinafter referred to as "448 occc" is obtained, and then 448 occc is reacted with sodium methoxide.
  • a method of dehydrating 448 occc to obtain 1437 dycc is disclosed.
  • the reaction product produced by the above-mentioned method includes 1437-chloro-3,3,4,4,5,5-hexafluoro- produced by further dehydrofluorination of 1437 dycc. It was found to contain 1-pentyne. This 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne has the problem of reducing the thermal and chemical stability of 1437 dycc. In order not to cause such an undesirable problem, it is preferable to reduce the amount of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne that coexists with 1437 dycc as much as possible.
  • water may be mixed and the reaction product may contain water.
  • water moisture
  • a solvent, a refrigerant, a foaming agent or an aerosol when it is used as a cleaning agent, a solvent, a refrigerant, a foaming agent or an aerosol, reliability and performance may be deteriorated and various problems may be caused.
  • the present invention has been made in order to solve the above-mentioned problems. From a composition containing 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water, A process for producing 1437 dycc that can efficiently remove chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water, has a high recovery rate of 1437 dycc, and increases the purity of 1437 dycc. The purpose is to provide.
  • the present invention provides a method for manufacturing 1437 dycc having the following configuration.
  • a distillation composition containing 1437 dycc, water and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne was distilled to give 1-chloro-3,3,4 , 4, 5, 5-hexafluoro-1-pentyne and water are removed, 1437 dycc manufacturing method characterized by the above-mentioned.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water are removed by forming an azeotrope or azeotrope-like composition,
  • the distillation composition is prepared using a reaction composition obtained by dehydrofluorination of 1-chloro-2,2,3,3,4,4,5,5-octafluoropentane. [1] to [6].
  • the distillation is performed using a distillation column, and the distillation conditions of the distillation column are a column top temperature of 10 to 95 ° C., and a column pressure of 50 to 760 mmHg, [1] to [7] The manufacturing method as described in.
  • the method for producing 1437 dycc of the present invention from a composition containing 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water, 1-chloro-3,3 , 4, 4, 5, 5-hexafluoro-1-pentyne and water can be efficiently removed. Therefore, the recovery rate of 1437 dycc can be increased and the purity of 1437 dycc can be increased.
  • Embodiments of the present invention will be described below.
  • a distillation composition containing 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is distilled, and the distillation Remove 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water from the composition.
  • 1437 dycc is purified by removing 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water from the above-described distillation composition.
  • a composition having an increased purity of 1437 dycc can be produced.
  • a part of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water in the distillation composition may be removed, or all of them may be removed. May be.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water in the composition for distillation are azeotropic compositions during distillation of the composition for distillation. Alternatively, it is preferably removed from the distillation composition by forming an azeotrope-like composition.
  • an azeotropic composition is a mixture of two or more compounds, in which the composition of the gas phase generated by vaporization of the liquid phase is the same as the composition of the liquid phase or by liquefaction of the gas phase.
  • the composition of the liquid phase produced is the same as the composition of the gas phase.
  • An azeotropic composition can be suitably used for distillation and reflux because the composition does not change due to evaporation or condensation. Note that the composition of the azeotropic composition varies depending on the pressure condition.
  • the azeotrope-like composition behaves similarly to the azeotrope composition. That is, in the azeotrope-like composition, the composition of the gas phase generated by vaporization of the liquid phase is substantially the same as the composition of the liquid phase, or the composition of the liquid phase generated by liquefaction of the gas phase is the gas phase.
  • the composition is substantially the same. Since an azeotrope-like composition hardly changes in composition due to evaporation and condensation, it can be suitably used for distillation and reflux as in the case of an azeotrope composition.
  • the present inventors have found that 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water form an azeotropic composition or an azeotrope-like composition. Further, the azeotrope or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is an azeotrope of 1437 dycc and water. Or it has been found that it is formed in preference to an azeotrope-like composition.
  • the azeotropic or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water has a lower boiling point than 1437 dycc. That is, the boiling point of 1437 dycc is about 89 ° C., whereas the azeotropic composition or azeotrope of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water
  • the boiling point of the composition is about 65 to 85 ° C.
  • the boiling point is a boiling point under atmospheric pressure. The atmospheric pressure is 101.325 kPa.
  • An azeotropic composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is 1-chloro-3 represented by the following formula (1) under atmospheric pressure.
  • 3,4,4,5,5-hexafluoro-1-pentyne has a relative volatility of 1.00 and 1-chloro-3,3,4,4,5,5-hexafluoro-1 -
  • the azeotrope-like composition of pentine and water has a relative volatility represented by the following formula (1) within a range of 1.00 ⁇ 0.20.
  • the azeotrope-like composition can obtain substantially the same effect as the azeotrope composition as long as the relative volatility is within the above range.
  • the composition range in which the desired relative volatility can be obtained can be obtained as follows. First, the composition of the mixture of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is gradually changed, and the composition of the liquid phase and the gas phase is changed to a Karl Fischer moisture meter. Or, measure by gas chromatograph. Using this liquid phase and gas phase composition, the relative volatility is determined from the above formula (1). Thereby, the correlation with a composition and a relative volatility is calculated
  • the azeotropic and azeotrope-like compositions of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water are 1-chloro-3,3,4,4,
  • the ratio of the amount of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne to the total amount of 5,5-hexafluoro-1-pentyne and water is 0.001 to 15% by mass It is preferable that When the ratio is within the above range, the relative volatility tends to be within the range of 1.00 ⁇ 0.20, and the boiling point tends to be about 65 to 85 ° C. From the viewpoint of reducing the boiling point by bringing the relative volatility closer to 1.00, the above ratio is more preferably 0.01 to 10% by mass, further preferably 0.05 to 5% by mass. It is particularly preferably 5 to 3% by mass.
  • the distillation composition contains 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne, and water.
  • the composition for distillation is not particularly limited as long as it is a composition containing 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water. Further, the distillation composition may contain components other than 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne, and water.
  • the composition for distillation may be liquid or gas.
  • 1437 dycc there are Z-form and E-form which are geometric isomers depending on the position of the substituent on the double bond.
  • 1437 dycc of the composition for distillation used in this embodiment may be either Z-form (1437 dycc (Z)) or E-form (1437 dycc (E)), and a mixture of 1437 dycc (Z) and 1437 dycc (E). It may be.
  • a mixture of 1437 dycc (Z) and 1437 dycc (E) a mixture of 1437 dycc (Z) is preferably 50% or more, more preferably 90% or more, and still more preferably 95% or more.
  • the composition for distillation is selected from 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water, which are produced when 1437 dycc is obtained by the method described later. It can prepare using the reaction composition containing at least 1 sort (s). That is, when 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water are contained in the reaction product formed when obtaining 1437 dycc, this reaction product The product can be used as a composition for distillation as it is.
  • compositions obtained by washing the reaction product with water or alkali to remove acidic substances such as hydrogen fluoride and hydrogen chloride contained in the reaction product may be used as the composition for distillation.
  • “preparing” a composition includes the case where the above-described reaction composition or the like is used as it is.
  • the dehydrofluorination reaction can be performed by either a liquid phase reaction or a gas phase reaction.
  • the dehydrofluorination reaction in a liquid phase reaction refers to the dehydrofluorination reaction of 448 occc in a liquid state.
  • the dehydrofluorination reaction in a gas phase reaction means the dehydrofluorination reaction of 448 occc in a gaseous state.
  • the 448 occc dehydrofluorination reaction is preferably performed by a liquid phase reaction in terms of reaction efficiency.
  • the base may be any base that can perform the dehydrofluorination reaction, and examples thereof include metal hydroxides, metal oxides, metal carbonates, and metal alkoxides.
  • a base may be used individually by 1 type and may use 2 or more types together.
  • metal hydroxides include alkali metal hydroxides and alkaline earth metal hydroxides.
  • alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • metal oxides include alkali metal oxides and alkaline earth metal oxides.
  • alkali metal oxide include sodium oxide.
  • alkaline earth metal oxide include calcium oxide.
  • metal carbonates include alkali metal carbonates and alkaline earth metal carbonates.
  • alkali metal carbonate include lithium, sodium or potassium carbonate.
  • Alkaline earth metal carbonates include beryllium, magnesium, calcium, strontium or barium carbonate.
  • Examples of the metal alkoxide include alkali metal alkoxides.
  • Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide.
  • metal hydroxides are preferable and potassium hydroxide and sodium hydroxide are more preferable because they are easy to handle and have high reactivity.
  • the above metal hydroxide is preferably used because of its high solubility in water.
  • the dehydrofluorination reaction is performed by a liquid phase reaction, it is preferably performed in the presence of a phase transfer catalyst in order to increase the reaction rate.
  • phase transfer catalyst examples include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers, quaternary ammonium salts, quaternary phosphonium salts, fourth compounds.
  • a quaternary arsonium salt and a sulfonium salt are preferable, and a quaternary ammonium salt is more preferable.
  • quaternary ammonium salt examples include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), and methyltri-n-octylammonium chloride (TOMAC).
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • quaternary phosphonium salt examples include tetraethylphosphonium ion, tetra-n-butylphosphonium ion, ethyltri-n-octylphosphonium ion, cetyltriethylphosphonium ion, cetyltri-n-butylphosphonium ion, n-butyltriphenylphosphonium.
  • quaternary arsonium salt examples include triphenylmethylarsonium fluoride, tetraphenylarsonium fluoride, triphenylmethylarsonium chloride, tetraphenylarsonium chloride, and tetraphenylarsonium bromide.
  • the sulfonium salt include di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, dihexylmethylsulfonium iodide, dicyclohexylmethylsulfonium iodide, dodecylmethylethylsulfonium chloride, tris (diethylamino) Examples include sulfonium difluorotrimethyl silicate.
  • crown ether examples include 18-crown-6, dibenzo-18-crown-6, and dicyclohexyl-18-crown-6.
  • phase transfer catalysts TBAC, TBAB, and TOMAC are preferred from the viewpoint of industrial availability, price, ease of handling, and reactivity.
  • the 448 occc dehydrofluorination reaction when carried out by a gas phase reaction, it can be carried out in the presence of activated carbon or a metal catalyst.
  • the specific surface area of the activated carbon used in the gas phase reaction from the viewpoint of improving the reaction conversion rate and the by-product suppression, preferably 10 ⁇ 3000m 2 / g, more preferably 20 ⁇ 2500m 2 / g, 50 ⁇ 2000m 2 / g is more preferable.
  • the specific surface area of the activated carbon is measured by a method based on the BET method.
  • activated carbon examples include activated carbon prepared from charcoal, coal, coconut shells, and the like. More specifically, there are formed coal having a length of about 2 to 5 mm, crushed coal having a length of about 4 to 50 mesh, granular coal, and powdered coal.
  • the amount of water in the activated carbon is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass when the total amount of activated carbon and moisture is 100% by mass from the viewpoint of improving reactivity and selectivity. % Or less is more preferable.
  • metal catalysts include zero-valent iron, zero-valent cobalt, zero-valent nickel, zero-valent palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, tin oxide, magnesium oxide, and oxidation.
  • metal catalysts include zero-valent iron, zero-valent cobalt, zero-valent nickel, zero-valent palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, tin oxide, magnesium oxide, and oxidation.
  • examples thereof include lanthanum, nickel oxide, aluminum fluoride oxide, chromium fluoride oxide, magnesium fluoride oxide, lanthanum oxide fluoride, alkali metal halide, alkaline earth metal halide, and chromium hydroxide.
  • activated carbon or an alkaline earth metal fluoride from the viewpoint of improving the reactivity and selectivity. More preferably, activated carbon, BaF 2 , SrF 2 , or CaF 2 is used.
  • the reaction product obtained by the 448 occc dehydrofluorination reaction is usually 1-chloro-3,3,4,4,5,5- produced by further dehydrofluorination of 1437 dycc. Contains hexafluoro-1-pentyne. Further, water mixed in the 448 occc dehydrofluorination reaction may be included in the reaction product. That is, a reaction containing 1437 dycc and at least one selected from 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water by the 448 occc dehydrofluorination reaction A composition is obtained.
  • the reaction composition obtained by the above method may be used as it is as a composition for distillation, or water, 1-chloro-3,3,4,4,5,5-hexafluoro contained in the reaction composition. Distilled one prepared by adding at least one selected from 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water according to the content of -1-pentyne It may be used as a composition.
  • reaction composition a reaction composition containing 1437 dycc and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and not containing water (first reaction composition) And a reaction composition (second reaction composition) containing 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne, and water.
  • the first reaction composition that is, the reaction composition containing 1437 dycc and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and no water
  • a composition for distillation can be obtained.
  • the distillation is carried out as it is.
  • Composition ie, 1437 dycc, water, and reaction composition containing 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne
  • water can be added to the second reaction composition depending on the content of water and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne.
  • the content of 1437 dycc in the distillation composition used in this embodiment is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass with respect to the total amount of the distillation composition. The above is more preferable. If the content of 1437 dycc is not less than the above lower limit, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water can be efficiently removed, and 1437 dycc in the bottoms can be removed. The recovery rate can be increased.
  • the contents of water and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne in the distillation composition are not necessarily limited.
  • water and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne in the distillation composition water and 1-chloro-3,3,4,4, An azeotropic or azeotrope-like composition can be formed from 5,5-hexafluoro-1-pentyne.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water in the distillation composition all form an azeotropic composition or an azeotrope-like composition. It is preferably removed efficiently from the composition for use.
  • the 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne content and the total water content of 1-chloro-3 The content ratio of ⁇ 3, 3, 4, 4, 5, 5-hexafluoro-1-pentyne is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass.
  • the content is 0.05 to 5% by mass, and particularly preferably 1.5 to 3% by mass.
  • the proportion of water in the composition for distillation can be prepared by adding water.
  • the ratio of water can be increased by adding water.
  • the composition for distillation may contain components other than 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water.
  • 1437 dycc is obtained by dehydrofluorination reaction of raw materials and 448 occc to produce 1437 dycc. Examples of the by-products generated in addition to 1437 dycc and 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne in the obtaining step.
  • Examples of components other than 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water that can be included in the distillation composition include 448 occc, 3,3 , 4,4,5,5-hexafluoro-1-pentyne, 1,1,2,2,3,3,4,4,5-nonafluoropentane, 2,3,3,4,4,5, Examples include 5-heptafluoro-1-pentene, 1,2,3,3,4,4,5,5-octafluoro-1-pentene, and alcohols such as OFPO and methanol.
  • Ingredients other than 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water are based on the total amount of the composition for distillation from the viewpoint of increasing the recovery rate of 1437 dycc. It is preferably 30% by mass or less, and more preferably 10% by mass or less.
  • alcohols such as OFPO and methanol may inhibit the formation of an azeotropic composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water, When these compounds are included, the content is preferably 5% by mass or less, more preferably 1% by mass or less, based on the total amount of the distillation composition.
  • distillation In the method for producing 1437 dycc of this embodiment, a distillation composition containing 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is distilled.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water can form an azeotropic or azeotrope-like composition.
  • the boiling point of 1437 dycc is higher than the boiling point of the azeotropic or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water. Since the distillation composition is distilled, an azeotropic composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water from the distillation composition or At least a portion of the azeotrope-like composition can be removed.
  • composition having a reduced content of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water that is, a composition having an increased purity of 1437 dycc is obtained.
  • the distillation apparatus removes at least a part of an azeotropic or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water from the distillation composition. Any known distillation apparatus can be used as long as it can be removed.
  • FIG. 1 shows an example of a distillation apparatus.
  • the distillation apparatus 10 includes, for example, a distillation column 11.
  • the distillation column 11 includes a pipe 12 for supplying a distillation composition, a pipe 13 for taking a distillate from the top of the distillation tower 11, and a distillation tower. 11 is connected to a piping 14 for taking out the bottoms from the tower bottom.
  • the distillation apparatus 10 may be either a batch type or a continuous type.
  • the distillation column 11 may be either a hollow type or a multistage type.
  • a distillate containing the product can be obtained.
  • the bottoms containing 1437 dycc can be obtained from the tower bottom.
  • composition for distillation exceeds the composition range of the azeotrope or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water.
  • 5,5-hexafluoro-1-pentyne or water may be contained in, for example, bottoms from the bottom of the column.
  • the composition for distillation is usually supplied to the middle stage of the multistage distillation column 10.
  • the distillate containing an azeotropic or azeotrope-like composition of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water is a composition for distillation. It can be obtained from the stage above the stage where the product is fed. Moreover, the bottom product containing 1437 dycc can be obtained from the stage below the stage to which the composition for distillation is supplied.
  • the pressure during distillation is preferably 50 to 760 mmHg in absolute pressure, more preferably 100 to 500 mmHg, and further preferably 200 to 400 mmHg.
  • the top temperature of the distillation column is preferably 10 to 95 ° C.
  • the top temperature of the distillation column is azeotropic with 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water.
  • the top temperature of the distillation column is azeotropic with 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water.
  • it is preferably 40 ° C. or higher, more preferably 43 ° C. or higher, 45 More preferably, it is not lower than ° C.
  • 60 degrees C or less is preferable, 57 degrees C or less is more preferable, 55 degrees C or less is further more preferable.
  • Distillation can be performed again using the bottoms containing 1437 dycc as the composition for distillation.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water are contained in the bottom product, 1-chloro-3,3,4,4 is obtained by distillation.
  • 4,5,5-Hexafluoro-1-pentyne and water can be separated, and a bottom product with an increased purity of 1437 dycc can be obtained.
  • the recovery rate of bottoms can be made into 85% or more by distilling, for example.
  • the recovery rate of the bottoms is preferably 90% or more, more preferably 95% or more.
  • the recovery rate of 1437 dycc in a bottom can be made 90% or more by distilling, for example.
  • the recovery rate of 1437 dycc in the bottoms is preferably 93% or more, more preferably 95% or more.
  • the recovery rate [%] of the bottoms can be obtained by the following formula from the amount of 1437 dycc in the composition for distillation and the amount of 1437 dycc in the bottoms.
  • 1437 dycc relative to the sum of the contents of 1437 dycc, 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water in the bottoms.
  • the content ratio (purity of 1437 dycc) can be 85% by mass or more. 90 mass% or more is preferable, as for the said ratio, 95 mass% or more is more preferable, 98 mass% or more is further more preferable, and 99 mass% is the most preferable.
  • the content of 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne in the bottoms is preferably 1000 ppm or less, preferably 100 ppm or less with respect to the content of 1437 dycc. More preferably it is.
  • the water content in the bottoms can be reduced.
  • the content of water in the bottoms after contact with the solid adsorbent is preferably 1000 ppm or less, more preferably 100 ppm or less, based on the total content of 1437 dycc.
  • Example 1 448 occc and tetra-n-butylammonium bromide (TBAB) were put into a reactor, and a 34 mass% potassium hydroxide (KOH) aqueous solution was added dropwise to carry out a 448 occc dehydrofluorination reaction at 30 ° C. After reacting for 8 hours, the organic layer was recovered to obtain a composition for distillation.
  • a distillation column a multistage distillation column having 50 theoretical plates was prepared. The distillation composition was supplied at a supply rate of 1.0 kg / h from the 20th stage from the top of the distillation column.
  • 1437 dycc (Z) is 0.98 kg / h
  • water is 0.0080 kg / h
  • 1437 dycc (E) is 0.010 kg / h
  • 1-chloro-3, 3,4,4,5,5-hexafluoro-1-pentyne (indicated in the following Tables 1 to 4 as “pentine”) was supplied at 0.0010 kg / h.
  • continuous distillation was performed at an operating pressure of 300 mmHg and a tower top temperature of 50.0 ⁇ 0.5 ° C.
  • the distillate was extracted from the top of the column and the bottom was extracted from the bottom.
  • the amount of water recovered is determined using a Karl Fischer moisture meter, and 1437 dycc (Z), 1437 dycc (E) and 1-chloro-3, The recovered amount of 3,4,4,5,5-hexafluoro-1-pentyne was determined. Further, the recovery rate (recovery amount / supply amount) was determined from the supply amount and the recovery amount.
  • Table 1 shows the supply amount of the composition for distillation, and also shows the recovery amount and recovery rate of the distillate and the bottom product.
  • Table 2 also shows the composition of the distillation composition, distillate and bottom product (1437 dycc (Z), 1437 dycc (E) or 1-chloro-3,3,4,4,5,5-hexafluoro- 1-pentyne content ratio).
  • composition of the composition for distillation is calculated
  • composition of the distillate and the bottom product is determined from the recovered amount of each component.
  • Example 2 As shown in Table 3, the amount of each component in the composition for distillation was changed, and distillation and measurement were performed in the same manner as in Example 1.
  • Table 3 shows the recovery amount and recovery rate of the distillate and the bottom product, respectively.
  • Table 4 shows the composition of the distillation composition, the distillate, and the bottom product, respectively.
  • the recovery rate of the product can be 91% by mass or more, and the content ratio of 1437 dycc in the product can be 98% by mass or more.
  • 1-chloro-3,3,4,4,5,5-hexafluoro-1-pentyne and water can be efficiently removed, the recovery rate of 1437 dycc can be increased, and the purity of 1437 dycc can be achieved. Can be increased. For this reason, it can be effectively used in a wide range of fields such as cleaning agents, solvents, refrigerants and the like using 1437 dycc.
  • the entire contents of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2018-103737 filed on May 30, 2018 are cited herein as disclosure of the specification of the present invention. Incorporated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène, au moyen duquel il devient possible d'éliminer du 1-chloro-3,3,4,4,5,5-hexafluoro-1-penthyne et de l'eau avec une efficacité élevée, et d'obtenir un taux de collecte élevé de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène, et d'augmenter également la pureté du 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène. Le procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène, est caractérisé en ce qu'une composition de distillation comprenant du 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène, de l'eau et du 1-chloro-3,3,4,4,4,5,5-hexafluoro-1-penthyne est distillée pour éliminer 1-chloro-3,3,4,4,5,5-hexafluoro-1-penthyne et l'eau.
PCT/JP2019/021400 2018-05-30 2019-05-29 Procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène WO2019230842A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2020522270A JP7314934B2 (ja) 2018-05-30 2019-05-29 １－クロロ－２，３，３，４，４，５，５－ヘプタフルオロ－１－ペンテンの製造方法
CN201980035670.8A CN112204003B (zh) 2018-05-30 2019-05-29 1-氯-2,3,3,4,4,5,5-七氟-1-戊烯的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-103779 2018-05-30
JP2018103779 2018-05-30

Publications (1)

Publication Number Publication Date
WO2019230842A1 true WO2019230842A1 (fr) 2019-12-05

Family

ID=68698262

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/021400 WO2019230842A1 (fr) 2018-05-30 2019-05-29 Procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène

Country Status (3)

Country Link
JP (1) JP7314934B2 (fr)
CN (1) CN112204003B (fr)
WO (1) WO2019230842A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11254824B2 (en) * 2017-08-25 2022-02-22 AGC Inc. Solvent composition, cleaning method, method for producing substrate with coating film, and heat transfer fluid
CN116120149A (zh) * 2023-04-04 2023-05-16 北京宇极科技发展有限公司 饱和卤代烃脱卤化氢制备含氟炔的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013525486A (ja) * 2010-05-06 2013-06-20 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロプロペン及び水の共沸混合物様の組成物
JP2013529234A (ja) * 2010-05-06 2013-07-18 ハネウェル・インターナショナル・インコーポレーテッド ペンタフルオロプロペン及び水の共沸混合物様の組成物
JP2015518898A (ja) * 2012-06-06 2015-07-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ フルオロオレフィン類中のＲｆＣＣＸ不純物の低減のための方法
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4271822B2 (ja) * 2000-02-29 2009-06-03 独立行政法人産業技術総合研究所 １−クロロヘプタフルオロシクロペンテンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013525486A (ja) * 2010-05-06 2013-06-20 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロプロペン及び水の共沸混合物様の組成物
JP2013529234A (ja) * 2010-05-06 2013-07-18 ハネウェル・インターナショナル・インコーポレーテッド ペンタフルオロプロペン及び水の共沸混合物様の組成物
JP2015518898A (ja) * 2012-06-06 2015-07-06 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ フルオロオレフィン類中のＲｆＣＣＸ不純物の低減のための方法
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZAPEVALOV, A. YA. ET AL.: "a, a-Disubstituted polyfluoroalkenes", ZHURNAL ORGANICHESKOI KHIMII, vol. 24, no. 8, 1988, pages 1626 - 1633, XP008110423, ISSN: 0514-7492 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11254824B2 (en) * 2017-08-25 2022-02-22 AGC Inc. Solvent composition, cleaning method, method for producing substrate with coating film, and heat transfer fluid
CN116120149A (zh) * 2023-04-04 2023-05-16 北京宇极科技发展有限公司 饱和卤代烃脱卤化氢制备含氟炔的方法

Also Published As

Publication number Publication date
JP7314934B2 (ja) 2023-07-26
CN112204003A (zh) 2021-01-08
CN112204003B (zh) 2023-09-29
JPWO2019230842A1 (ja) 2021-06-24

Similar Documents

Publication Publication Date Title
KR101879787B1 (ko) 2,3,3,3-테트라플루오로프로펜 제조방법
KR101655257B1 (ko) 2-클로로-3,3,3-트리플루오로프로펜(ＨＣＦＣ-1233ｘｆ), 2-클로로-1,1,1,2-테트라플루오로프로판(ＨＣＦＣ-244ｂｂ), 및 하이드로겐 플루오라이드(ＨＦ)의 공비 조성물
CN107382657B (zh) 制备四氟丙烯的方法
WO2017018412A1 (fr) Procédé de production de 1-chloro-2,3,3-trifluoropropène
WO2010074254A1 (fr) Procédés de préparation de 1,1-dichloro-2,3,3,3-tétrafluoropropène et de 2,3,3,3-tétrafluoropropène
US8212092B2 (en) Process for the reduction of acidic contaminates in fluorinated hydrocarbons
JP6168068B2 (ja) テトラフルオロプロペンの精製方法
JP7115611B2 (ja) 組成物
JP6245259B2 (ja) （ｅ）−１−クロロ−３，３，３−トリフルオロプロペンの製造方法
WO2013154059A1 (fr) Composition azéotropique ou de type azéotrope, et procédé de production de 2,3,3,3-tétrafluoropropène ou de chlorométhane
WO2019230842A1 (fr) Procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène
CN110023272B (zh) 1-氯-2,3,3-三氟丙烯的制造方法
CN102947258A (zh) 1,1-二氯-2,2,3,3,3-五氟丙烷的制造方法
WO2019230844A1 (fr) Procédé de production de (z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentène
JP2010090045A (ja) フッ化水素の分離方法
CN108911946B (zh) 一种离子液体用于脱除氟代化合物中hf的方法
WO2021187369A1 (fr) Procédé de production d'un (hydro)halocarbure
JP2015224236A (ja) （ｅ）−１−クロロ−３，３，３−トリフルオロプロペンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19811664

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020522270

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19811664

Country of ref document: EP

Kind code of ref document: A1